2021, Tilgner, Andreas, Schaefer, Thomas, Alexander, Becky, Barth, Mary, Collett, Jeffrey L., Fahey, Kathleen M., Nenes, Athanasios, Pye, Havala O.T., Herrmann, Hartmut, McNeill, V. Faye

The acidity of aqueous atmospheric solutions is a key parameter driving both the partitioning of semi-volatile acidic and basic trace gases and their aqueous-phase chemistry. In addition, the acidity of atmospheric aqueous phases, e.g., deliquesced aerosol particles, cloud, and fog droplets, is also dictated by aqueous-phase chemistry. These feedbacks between acidity and chemistry have crucial implications for the tropospheric lifetime of air pollutants, atmospheric composition, deposition to terrestrial and oceanic ecosystems, visibility, climate, and human health. Atmospheric research has made substantial progress in understanding feedbacks between acidity and multiphase chemistry during recent decades. This paper reviews the current state of knowledge on these feedbacks with a focus on aerosol and cloud systems, which involve both inorganic and organic aqueous-phase chemistry. Here, we describe the impacts of acidity on the phase partitioning of acidic and basic gases and buffering phenomena. Next, we review feedbacks of different acidity regimes on key chemical reaction mechanisms and kinetics, as well as uncertainties and chemical subsystems with incomplete information. Finally, we discuss atmospheric implications and highlight the need for future investigations, particularly with respect to reducing emissions of key acid precursors in a changing world, and the need for advancements in field and laboratory measurements and model tools.

2021, Cox, R. Anthony, Ammann, Markus, Crowley, John N., Griffiths, Paul T., Herrmann, Hartmut, Hoffmann, Erik H., Jenkin, Michael E., McNeill, V. Faye, Mellouki, Abdelwahid, Penkett, Christopher J., Tilgner, Andreas, Wallington, Timothy J.

The term open-air factor (OAF) was coined following microbiological research in the 1960s and 1970s which established that rural air had powerful germicidal properties and attributed this to Criegee intermediates formed in the reaction of ozone with alkenes. We have re-evaluated those early experiments applying the current state of knowledge of ozone-alkene reactions. Contrary to previous speculation, neither Criegee intermediates nor the HO radicals formed in their decomposition are directly responsible for the germicidal activity attributed to the OAF. We identify other potential candidates, which are formed in ozone-alkene reactions and have known (and likely) germicidal properties, but the compounds responsible for the OAF remain a mystery. There has been very little research into the OAF since the 1970s, and this effect seems to have been largely forgotten. In this opinion piece we remind the community of the germicidal open-air factor. Given the current global pandemic spread by an airborne pathogen, understanding the natural germicidal effects of ambient air, solving the mystery of the open-air factor and determining how this effect can be used to improve human welfare should be a high priority for the atmospheric science community. © 2021 The Author(s).

2018, Karnezi, Eleni, Murphy, Benjamin N., Poulain, Laurent, Herrmann, Hartmut, Wiedensohler, Alfred, Rubach, Florian, Kiendler-Scharr, Astrid, Mentel, Thomas F., Pandis, Spyros N.

A lot of effort has been made to understand and constrain the atmospheric aging of the organic aerosol (OA). Different parameterizations of the organic aerosol formation and evolution in the two-dimensional volatility basis set (2D-VBS) framework are evaluated using ground and airborne measurements collected in the 2012 Pan-European Gas AeroSOls-climate interaction Study (PEGASOS) field campaign in the Po Valley (Italy). A number of chemical aging schemes are examined, taking into account various functionalization and fragmentation pathways for biogenic and anthropogenic OA components. Model predictions and measurements, both at the ground and aloft, indicate a relatively oxidized OA with little average diurnal variation. Total OA concentration and O: C ratios are reproduced within experimental error by a number of chemical aging schemes. Anthropogenic secondary OA (SOA) is predicted to contribute 15-25% of the total OA, while SOA from intermediate volatility compound oxidation contributes another 20-35%. Biogenic SOA (bSOA) contributions varied from 15 to 45% depending on the modeling scheme. Primary OA contributed around 5% for all schemes and was comparable to the hydrocarbon-like OA (HOA) concentrations derived from the positive matrix factorization of the aerosol mass spectrometer (PMF-AMS) ground measurements. The average OA and O: C diurnal variation and their vertical profiles showed a surprisingly modest sensitivity to the assumed vaporization enthalpy for all aging schemes. This can be explained by the interplay between the partitioning of the semi-volatile compounds and their gas-phase chemical aging reactions.

2017, Mu, Qing, Lammel, Gerhard, Gencarelli, Christian N., Hedgecock, Ian M., Chen, Ying, Přibylová, Petra, Teich, Monique, Zhang, Yuxuan, Zheng, Guangjie, van Pinxteren, Dominik, Zhang, Qiang, Herrmann, Hartmut, Shiraiwa, Manabu, Spichtinger, Peter, Su, Hang, Pöschl, Ulrich, Cheng, Yafang

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRF-Chem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

2021, Hartmann, Markus, Gong, Xianda, Kecorius, Simonas, van Pinxteren, Manuela, Vogl, Teresa, Welti, André, Wex, Heike, Zeppenfeld, Sebastian, Herrmann, Hartmut, Wiedensohler, Alfred, Stratmann, Frank

Ice-nucleating particles (INPs) initiate the primary ice formation in clouds at temperatures above ca. -38gC and have an impact on precipitation formation, cloud optical properties, and cloud persistence. Despite their roles in both weather and climate, INPs are not well characterized, especially in remote regions such as the Arctic. We present results from a ship-based campaign to the European Arctic during May to July 2017. We deployed a filter sampler and a continuous-flow diffusion chamber for offline and online INP analyses, respectively. We also investigated the ice nucleation properties of samples from different environmental compartments, i.e., the sea surface microlayer (SML), the bulk seawater (BSW), and fog water. Concentrations of INPs (NINP) in the air vary between 2 to 3 orders of magnitudes at any particular temperature and are, except for the temperatures above -10gC and below -32gC, lower than in midlatitudes. In these temperature ranges, INP concentrations are the same or even higher than in the midlatitudes. By heating of the filter samples to 95gC for 1ĝ€¯h, we found a significant reduction in ice nucleation activity, i.e., indications that the INPs active at warmer temperatures are biogenic. At colder temperatures the INP population was likely dominated by mineral dust. The SML was found to be enriched in INPs compared to the BSW in almost all samples. The enrichment factor (EF) varied mostly between 1 and 10, but EFs as high as 94.97 were also observed. Filtration of the seawater samples with 0.2ĝ€¯μm syringe filters led to a significant reduction in ice activity, indicating the INPs are larger and/or are associated with particles larger than 0.2ĝ€¯μm. A closure study showed that aerosolization of SML and/or seawater alone cannot explain the observed airborne NINP unless significant enrichment of INP by a factor of 105 takes place during the transfer from the ocean surface to the atmosphere. In the fog water samples with -3.47gC, we observed the highest freezing onset of any sample. A closure study connecting NINP in fog water and the ambient NINP derived from the filter samples shows good agreement of the concentrations in both compartments, which indicates that INPs in the air are likely all activated into fog droplets during fog events. In a case study, we considered a situation during which the ship was located in the marginal sea ice zone and NINP levels in air and the SML were highest in the temperature range above -10gC. Chlorophyll a measurements by satellite remote sensing point towards the waters in the investigated region being biologically active. Similar slopes in the temperature spectra suggested a connection between the INP populations in the SML and the air. Air mass history had no influence on the observed airborne INP population. Therefore, we conclude that during the case study collected airborne INPs originated from a local biogenic probably marine source. © Author(s) 2021.

2021, Triesch, Nadja, van Pinxteren, Manuela, Frka, Sanja, Stolle, Christian, Spranger, Tobias, Hoffmann, Erik Hans, Gong, Xianda, Wex, Heike, Schulz-Bull, Detlef, Gasparovic, Blazenka, Herrmann, Hartmut

In the marine environment, measurements of lipids as representative species within different lipid classes have been performed to characterize their oceanic sources and their transfer from the ocean into the atmosphere to marine aerosol particles. The set of lipid classes includes hydrocarbons (HC); fatty acid methyl esters (ME); free fatty acids (FFA); alcohols (ALC); 1,3-diacylglycerols (1,3 DG); 1,2-diacylglycerols (1,2 DG); monoacylglycerols (MG); wax esters (WE); triacylglycerols (TG); and phospholipids (PP) including phosphatidylglycerols (PG), phosphatidylethanolamine (PE), phosphatidylcholines (PC), as well as glycolipids (GL) which cover sulfoquinovosyldiacylglycerols (SQDG), monogalactosyl-diacylglycerols (MGDG), digalactosyldiacylglycerols (DGDG) and sterols (ST). These introduced lipid classes have been analyzed in the dissolved and particulate fraction of seawater, differentiating between underlying water (ULW) and the sea surface microlayer (SML) on the one hand. On the other hand, they have been examined on ambient submicrometer aerosol particle samples (PM1) which were collected at the Cape Verde Atmospheric Observatory (CVAO) by applying concerted measurements. These different lipids are found in all marine compartments but in different compositions. Along the campaign, certain variabilities are observed for the concentration of dissolved (∑DLULW: 39.8–128.5 µg L−1, ∑DLSML: 55.7–121.5 µg L−1) and particulate (∑PLULW: 36.4–93.5 µg L−1, ∑PLSML: 61.0–118.1 µg L−1) lipids in the seawater of the tropical North Atlantic Ocean. Only slight SML enrichments are observed for the lipids with an enrichment factor EFSML of 1.1–1.4 (DL) and 1.0–1.7 (PL). On PM1 aerosol particles, a total lipid concentration between 75.2–219.5 ng m−3 (averaged: 119.9 ng m−3) is measured. As also bacteria – besides phytoplankton sources – influence the lipid concentrations in seawater and on the aerosol particles, the lipid abundance cannot be exclusively explained by the phytoplankton tracer (chlorophyll a). The concentration and enrichment of lipids in the SML are not related to physicochemical properties which describe the surface activity. On the aerosol particles, an EFaer (the enrichment factor on the submicrometer aerosol particles compared to the SML) between 9×104–7×105 is observed. Regarding the individual lipid groups on the aerosol particles, a statistically significant correlation (R2=0.45, p=0.028) was found between EFaer and lipophilicity (expressed by the KOW value), which was not present for the SML. But simple physicochemical descriptors are overall not sufficient to fully explain the transfer of lipids. As our findings show that additional processes such as formation and degradation influence the ocean–atmosphere transfer of both OM in general and of lipids in particular, they have to be considered in OM transfer models. Moreover, our data suggest that the extent of the enrichment of the lipid class constituents on the aerosol particles might be related to the distribution of the lipid within the bubble–air–water interface. The lipids TG and ALC which are preferably arranged within the bubble interface are transferred to the aerosol particles to the highest extent. Finally, the connection between ice nucleation particles (INPs) in seawater, which are already active at higher temperatures (−10 to −15 ∘C), and the lipid classes PE and FFA suggests that lipids formed in the ocean have the potential to contribute to (biogenic) INP activity when transferred into the atmosphere.

2017, Li, Jiarong, Wang, Xinfeng, Chen, Jianmin, Zhu, Chao, Li, Weijun, Li, Chengbao, Liu, Lu, Xu, Caihong, Wen, Liang, Xue, Likun, Wang, Wenxing, Ding, Aijun, Herrmann, Hartmut

The chemical composition of 39 cloud samples and droplet size distributions in 24 cloud events were investigated at the summit of Mt. Tai from July to October 2014. Inorganic ions, organic acids, metals, HCHO, H2O2, sulfur( IV), organic carbon, and elemental carbon as well as pH and electrical conductivity were analyzed. The acidity of the cloud water significantly decreased from a reported value of pH 3.86 during 2007-2008 (Guo et al., 2012) to pH 5.87 in the present study. The concentrations of nitrate and ammonium were both increased since 2007-2008, but the overcompensation of ammonium led to an increase in the mean pH value. The microphysical properties showed that cloud droplets were smaller than 26.0 μm and most were in the range of 6.0-9.0 μm at Mt. Tai. The maximum droplet number concentration (Nd) was associated with a droplet size of 7.0 μm. High liquid water content (LWC) values could facilitate the formation of larger cloud droplets and broadened the droplet size distribution. Cloud droplets exhibited a strong interaction with atmospheric aerosols. Higher PM2.5 levels resulted in higher concentrations of water-soluble ions and smaller sizes with increased numbers of cloud droplets. The lower pH values were likely to occur at higher PM2.5 concentrations. Clouds were an important sink for soluble materials in the atmosphere. The dilution effect of cloud water should be considered when estimating concentrations of soluble components in the cloud phase.

2021, Triesch, Nadja, van Pinxteren, Manuela, Engel, Anja, Herrmann, Hartmut

Measurements of free amino acids (FAAs) in the marine environment to elucidate their transfer from the ocean into the atmosphere, to marine aerosol particles and to clouds, were performed at the MarParCloud (marine biological production, organic aerosol particles and marine clouds: a process chain) campaign at the Cabo Verde islands in autumn 2017. According to physical and chemical specifications such as the behavior of air masses, particulate MSA concentrations and MSA=sulfate ratios, as well as particulate mass concentrations of dust tracers, aerosol particles predominantly of marine origin with low to medium dust influences were observed. FAAs were investigated in different compartments: they were examined in two types of seawater underlying water (ULW) and in the sea surface microlayer (SML), as well as in ambient marine size-segregated aerosol particle samples at two heights (ground height based at the Cape Verde Atmospheric Observatory, CVAO, and at 744m height on Mt. Verde) and in cloud water using concerted measurements. The ΣFAA concentration in the SML varied between 0.13 and 3.64 μmol L-1, whereas it was between 0.01 and 1.10 μmol L-1in the ULW; also, a strong enrichment of ΣFAA (EFSML: 1.1-298.4, average of 57.2) was found in the SML. In the submicron (0.05-1.2 μm) aerosol particles at the CVAO, the composition of FAAs was more complex, and higher atmospheric concentrations of ΣFAA (up to 6.3 ngm-3) compared to the supermicron (1.2-10 μm) aerosol particles (maximum of 0.5 ngm-3) were observed. The total ΣFAA concentration (PM10) was between 1.8 and 6.8 ngm-3and tended to increase during the campaign. Averaged ΣFAA concentrations in the aerosol particles on Mt. Verde were lower (submicron: 1.5 ngm-3; supermicron: 1.2 ngm-3) compared to the CVAO. A similar contribution percentage of ΣFAA to dissolved organic carbon (DOC) in the seawater (up to 7.6 %) and to water-soluble organic carbon (WSOC) in the submicron aerosol particles (up to 5.3 %) indicated a related transfer process of FAAs and DOC in the marine environment. Considering solely ocean-atmosphere transfer and neglecting atmospheric processing, high FAA enrichment factors were found in both aerosol particles in the submicron range (EFaer(ΣFAA):2×103-6×103) and medium enrichment factors in the supermicron range (EFaer(ΣFAA):1×101-3×101). In addition, indications for a biogenic FAA formation were observed. Furthermore, one striking finding was the high and varying FAA cloud water concentration (11.2-489.9 ngm-3), as well as enrichments (EFCW:4×103and 1×104compared to the SML and ULW, respectively), which were reported here for the first time. The abundance of inorganic marine tracers (sodium, methanesulfonic acid) in cloud water suggests an influence of oceanic sources on marine clouds. Finally, the varying composition of the FAAs in the different matrices shows that their abundance and ocean- atmosphere transfer are influenced by additional biotic and abiotic formation and degradation processes. Simple physicochemical parameters (e.g., surface activity) are not sufficient to describe the concentration and enrichments of the FAAs in the marine environment. For a precise representation in organic matter (OM) transfer models, further studies. © 2021 American Institute of Physics Inc.. All rights reserved.

2021, Poulain, Laurent, Fahlbusch, Benjamin, Spindler, Gerald, Mueller, Konrad, van Pinxteren, Dominik, Wu, Zhijun, Iinuma, Yoshiteru, Birmili, Wolfram, Wiedensohler, Alfred, Herrmann, Hartmut

The identification of different sources of the carbonaceous aerosol (organics and black carbon) was investigated at a mountain forest site located in central Germany from September to October 2010 to characterize incoming air masses during the Hill Cap Cloud Thuringia 2010 (HCCT-2010) experiment. The near-PM1 chemical composition, as measured by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), was dominated by organic aerosol (OA; 41 %) followed by sulfate (19 %) and nitrate (18 %). Source apportionment of the OA fraction was performed using the multilinear engine (ME-2) approach, resulting in the identification of the following five factors: hydrocarbon-like OA (HOA; 3 % of OA mass), biomass burning OA (BBOA; 13 %), semi-volatile-like OA (SV-OOA; 19 %), and two oxygenated OA (OOA) factors. The more oxidized OOA (MO-OOA, 28 %) was interpreted as being influenced by aged, polluted continental air masses, whereas the less oxidized OOA (LO-OOA, 37 %) was found to be more linked to aged biogenic sources. Equivalent black carbon (eBC), measured by a multi-angle absorption photometer (MAAP) represented 10 % of the total particulate matter (PM). The eBC was clearly associated with HOA, BBOA, and MO-OOA factors (all together R2=0.83). Therefore, eBC's contribution to each factor was achieved using a multi-linear regression model. More than half of the eBC (52 %) was associated with long-range transport (i.e., MO-OOA), whereas liquid fuel eBC (35 %) and biomass burning eBC (13 %) were associated with local emissions, leading to a complete apportionment of the carbonaceous aerosol. The separation between local and transported eBC was well supported by the mass size distribution of elemental carbon (EC) from Berner impactor samples. Air masses with the strongest marine influence, based on back trajectory analysis, corresponded with a low particle mass concentration (6.4–7.5 µg m−3) and organic fraction (≈30 %). However, they also had the largest contribution of primary OA (HOA ≈ 4 % and BBOA 15 %–20 %), which was associated with local emissions. Continental air masses had the highest mass concentration (11.4–12.6 µg m−3), and a larger fraction of oxygenated OA (≈45 %) indicated highly processed OA. The present results emphasize the key role played by long-range transport processes not only in the OA fraction but also in the eBC mass concentration and the importance of improving our knowledge on the identification of eBC sources.

2018, Schmale, Julia, Henning, Silvia, Decesari, Stefano, Henzing, Bas, Keskinen, Helmi, Sellegri, Karine, Ovadnevaite, Jurgita, Pöhlker, Mira L., Brito, Joel, Bougiatioti, Aikaterini, Kristensson, Adam, Kalivitis, Nikos, Stavroulas, Iasonas, Carbone, Samara, Jefferson, Anne, Park, Minsu, Schlag, Patrick, Iwamoto, Yoko, Aalto, Pasi, Äijälä, Mikko, Bukowiecki, Nicolas, Ehn, Mikael, Frank, Göran, Fröhlich, Roman, Frumau, Arnoud, Herrmann, Erik, Herrmann, Hartmut, Holzinger, Rupert, Kos, Gerard, Kulmala, Markku, Mihalopoulos, Nikolaos, Nenes, Athanasios, O'Dowd, Colin, Petäjä, Tuukka, Picard, David, Pöhlker, Christopher, Pöschl, Ulrich, Poulain, Laurent, Prévôt, André Stephan Henry, Swietlicki, Erik, Andreae, Meinrat O., Artaxo, Paulo, Wiedensohler, Alfred, Ogren, John, Matsuki, Atsushi, Yum, Seong Soo, Stratmann, Frank, Baltensperger, Urs, Gysel, Martin

Aerosol-cloud interactions (ACI) constitute the single largest uncertainty in anthropogenic radiative forcing. To reduce the uncertainties and gain more confidence in the simulation of ACI, models need to be evaluated against observations, in particular against measurements of cloud condensation nuclei (CCN). Here we present a data set - ready to be used for model validation - of long-term observations of CCN number concentrations, particle number size distributions and chemical composition from 12 sites on 3 continents. Studied environments include coastal background, rural background, alpine sites, remote forests and an urban surrounding. Expectedly, CCN characteristics are highly variable across site categories. However, they also vary within them, most strongly in the coastal background group, where CCN number concentrations can vary by up to a factor of 30 within one season. In terms of particle activation behaviour, most continental stations exhibit very similar activation ratios (relative to particles 20nm) across the range of 0.1 to 1.0% supersaturation. At the coastal sites the transition from particles being CCN inactive to becoming CCN active occurs over a wider range of the supersaturation spectrum. Several stations show strong seasonal cycles of CCN number concentrations and particle number size distributions, e.g. at Barrow (Arctic haze in spring), at the alpine stations (stronger influence of polluted boundary layer air masses in summer), the rain forest (wet and dry season) or Finokalia (wildfire influence in autumn). The rural background and urban sites exhibit relatively little variability throughout the year, while short-term variability can be high especially at the urban site. The average hygroscopicity parameter, calculated from the chemical composition of submicron particles was highest at the coastal site of Mace Head (0.6) and lowest at the rain forest station ATTO (0.2-0.3). We performed closure studies based on -Köhler theory to predict CCN number concentrations. The ratio of predicted to measured CCN concentrations is between 0.87 and 1.4 for five different types of . The temporal variability is also well captured, with Pearson correlation coefficients exceeding 0.87. Information on CCN number concentrations at many locations is important to better characterise ACI and their radiative forcing. But long-term comprehensive aerosol particle characterisations are labour intensive and costly. Hence, we recommend operating migrating-CCNCs to conduct collocated CCN number concentration and particle number size distribution measurements at individual locations throughout one year at least to derive a seasonally resolved hygroscopicity parameter. This way, CCN number concentrations can only be calculated based on continued particle number size distribution information and greater spatial coverage of long-term measurements can be achieved.